Azo dyestuffs



Patented Mar. 2?, 1954 AZO DYESTUFFS Hans Ruckstuhl, Otto Senn, andWalter Wehrli, Basel, Switzerland, assignors to Sandoz A. G., Basel,Switzerland, a Swiss firm No Drawing. Application June 19, 1951, SerialNo. 232,447

Claims priority, application Switzerland June 21, 1950 14 Claims. 1

The present invention relates to new azo dyestuffs and to thepreparation thereof.

A primary object of the invention is the embodiment of a new group ofazo dyestuffs char acterized by superior fastness properties, especially fastness to washing and to light. A further object of theinvention is the embodiment of azo dyestuifs, the dyeings of which ontextiles are in pure khaki shades so that the latter may be realizedwithout the use of mixed dyes as has heretofore been necessary whenproducing khaki dyeings with azo dyes.

These objects, and other which will hereinafter be evident, are realizedby the new azo dyestuffs according to the present invention, saiddyestuffs corresponding to the formula wherein R stands for an aryl, anarylazoaryl or an arylazo-arylazoaryl radical, one as stands for SOxHand the other as for hydrogen, Y stands for a metallizable group, Mestands for copper or chromium, n represents one of the integers 0, l, 2and 3 and wherein nucleus I may contain additional substituents, e. g.SO3H, N02, halogen,

lower alkyl and/or lower alkoxy.

These new azo dyestuffs are prepared, according to the presentinvention, by coupling the desired diazo compound with 1 mol of amonoazo dyestuif-as such or in the form of the metalcomplex-of thefollowing composition:

wherein one x stands for SOsI-I and the other :1: for hydrogen, and 1/stands for a metallizable group, and wherein nucleus I may containadditional substituents, e. g. SOsH, N02, halogen, lower alkyl and/orlower alkoxy, and if necessary treating the resultant disazo or polyazodye- The products obtained according to the precedingly describedprocess are valuable dyestuffs or are intermediates for the productionof such dyesutifs. They comprise an entire series which makes possiblethe achievement of pure khaki dyeings in shadeswhich have heretoforebeen obtainable by means of azo dyestuffs only when a mixture of thelatter has been employed.

A previously indicated, a wide variety of diazo compounds may beemployed in preparing the products of this invention. Illustrative ofsuch are the diazo compounds of, inter alia, 2 aminobenzene-l-carboxylicacid, 5-nitro-2-amino1- methoxybenzene,5-nitro-2-aminobenzene-l-carboxylic acid, 4'-amino-3-methoxy-5-methyl-4-hydroxy-l,1'-azobenzene-B-carboxylic acid, 2- hydroxybenzene 1carboxylic acid 4,4' diaminodiphenyl 1 amino 2 methoxy 5- methylbenzene,5 amino 2 hydroxybenzene- 1 carboxylic acid 3 sulfonic acid- 3 methyl- 1aminobenzene-fl amino 2 methoxy 5- methylbenzene, 2 hydroxybenzene lcarboxylic acid -4 (4' aminobenzoylamino) l aminobenzene l amino 2methoxy 5 methylbenzene, 2 naphthylamine 4,8 disulfonic acid 3 methyl 1aminobenzene-damino 2 methoxy 5 methylbenzene, 2- naphthylamine 6,8disulfonic acid-+3 methyl 1 aminobenzene- 1 amino 2 methoxy- 5methylbenzcne, etc.; the intermediates from one mol of tetrazotized4,4'-diaminodiphenyl and one mol of 2-hydroxybenzene-l-carboxylic acidor from one mol of tetrazotized 4,4'-diamino- 3,3'-dimethoxydiphenyl andone mol of any desired naphthol monosulfonic acid or naphthol disulfonicacid, etc. may also be used in this regard.

The trisazo and polyazo dyestuifs of the present invention aresuitablefor dyeing cotton and regenerated cellulose by the methodsconventionally used for direct dyestuffs. In. so far as the new productsare dyestuifs which contain free metallizable groups, their fastnessproperties can be improved by aftertreatment 0n the fiber with salts ofbivalent metals, especially with copper sulfate. In so far as the newproducts already contain metal in the molecule thereof, they canadvantageously be aftertreated with salts of bivalent copper in thepresence of polymeric substances containing imino or 1 amino groups,such as the substances described in Swiss Patents Nos. 253,709, 261,048,263,481 and 263,482; this treatment results in many cases in theattainment of outstanding wash fastness and light fastness properties.

The following examples illustrate the invention, without howeverlimiting the scope thereof. Parts and percentages are by weight. Theterm soda refers to sodium carbonate.

2,673,200 3 4 EXAMPLE'I Upon completion of the coupling which takes'I'he tetrazo compound from parts of 3 3'.. place, the pyridine isremoved and the Obtained dimethoxy-lAdiaminodiphenyl is coupled in17115310 dyestuff f the formula OaH alkaline medium with 30.3 parts ofl-hydroxyis purified by recrystallization. Dried andnaphthalene-3,8-disulfonic acid. The obtained ground, it is a darkpowder which dissolves in intermediate is then run into a solution ofthe water with a yellowish brown coloration and in disodium salt of 45.4parts of the monoazo dyeconcentrated sulfuric acid with a Bordeaux redstufi corresponding to the formula: coloration, and dyes cotton orregenerated cellu- OCHa OH lose in khaki-colored shades, the fastnesspropl l erties of which are improved by an after-cop- N=N- OH peringtreatment as described in Example 1.

By replacing the aforesaid monoazo dyestuff H038 by its copper complexand coupling the latter with the intermediate from 4,4'-diaminodiphenylsour and l-hydroxybenzene-2-carboxylic acid, ac-

in 400 parts of water and 1000 parts of pyridine. 95 cording to theprescriptions of the preceding Upon completion of the resultantcoupling, the paragraph, a dyestufi is obtained which dyes producedtrisazo dyestuff of the formula cotton in greenish khaki shades.

e I V N=N OH 0 CH3 mod on 0.11

HOzS- 0313 I is separated from the pyridine and purified by EXAMPLE- 3recrystallization. Dried and ground, it is a dark powder which dissolvesin water with a blue The tetrazo u d from 1 -4 pa t of 4,4-

coloration and in concentrated sulfuric acid 40 diaminodiphenyl is up W1 -8 parts of lwith a reddish blue coloration, and dyes cottonhydr0Xybenzene2warboxylic m d. nd th reor regenerated cellulose inreddish marine-blue Sultant ermed te is then reacted with the shades,the fastness properties of which are immonoazo dyestllfi described in pe 1 ac ordproved by aftercoppering, the copper complexing to theprescriptions set forth in the latter. ith Valuable dyestuff propertiesbeing prov The obtained dyestuif iS a dark powder which d d by b ilin thid t i dyestufi in D dissolves in water with a yellowish brown 001- dilte aqueous a mo ia, ith dditi of 75 oration and in concentrated sulfuricacid with parts of copper sulfate. 2. Bordeaux red coloration, and dyescotton or The copper complex compound corresponds to regeneratedcellulose in khaki-colored shades, the formula: the fastness propertiesof which are improved l l l A N=N o-ou-o O-Cu o 0311 HOaS I EXAMPLE 2 byaftercoppering with formation of the corre- The intermediate, producedby tetrazotizaspondmg copper m tion and coupling, from 18.4 parts of4,4-di- E-XAMPLE4 aminodiphenyl and 13.8 parts of 2-hydroxyben- 30.3parts of 2-aminonaphthalene-4,8-disulzoic acid, is run into a solutionof 46.8 parts of fonic acid are diazotized and coupled in acetic themonoazo dyestufi corresponding to the acid solution with 10.7 parts of3-amino-lformula methylbenzene. The obtained aminoazo dye- COOH v OHstufi is diazotized and coupled, in a medium I acidified with aceticacid, with 13.7 parts of 2- N=N OH amino-1-methoxy-4-methylbenzene.After further diazotization, the product is coupled with Ho3s- 46.8parts of the monoazo dyestuff described in 1 Example 2 according to theprescriptions set sotn forth in the latter. The resultant dyestufiis,

in 400 parts of Water and lOOOparts of pyridine. following purificationby recrystallization, a

dark powder which dissolves in water with brown coloration and inconcentrated sulfuric acid with violet coloration. It dyes cotton andregenerated cellulose in brown shades. The copper complex of thelast-named dyestuif-obtained in ammoniacal solution with the aid of 50parts of copper sulfate--yields khaki shades of excellent fastness tolight.

EXAMPLE 5 The diazo compound from 35.1 parts of 4'- amino 2 methyl lhydroxy 1,1 azobenzene-5-carboxy-3-sulfonic acid is coupled in aceticacid solution with 13.7 parts of 2-aminol-methyl-l-methoxybenzene. Theresultant intermediate is diazotized and coupled in pyridinecontainingsolution with the copper complexprepared in ammoniacal solution with theaid of copper sulfate-from 46.8 parts of the dyestuif of the formula:

SIO3H After isolation and drying of the reaction product, there isobtained a dark powder which dissolves in water with a brownish olivecoloration and concentrated sulfuric acid with a violet coloration. Itdyes cotton and regenerated cellulose in brown shades, the fastnessproperties of which are improved by aftertreatment with a salt ofbivalent copper, e. g. copper sulfate, in

the presence of thepolymeric substance which is obtained by condensingtriethylene tetramine with dicyandiamide according to the processdescribed in the Swiss Patent No. 253,709.

By introducing a second atom of copper into the dyestulf by means of atreatment with copper compounds splitting off the methoxy group, thereis obtaineda product of still better fastness properties.

EXAMPLE 6 trated sulfuric acid with a violet coloration. It

dyes cotton and regenerated cellulose in brownish khaki shades which,upon aftertreatment with a salt of bivalent copper, e. g. coppersulfate, in the presence of the polymeric substance obtainable bycondensing triethylene tetramine with dicyandiamide according to theprocess described in the Swiss Patent No. 253,709, are fast to light andto washing.

EXAMPLE 7 The tetrazo compound from 22.7 parts of 4-(4-arninobenzoylamino) -1-aminobenzene is first coupled in soda alkalinesolution with 13.8 parts of 1-hydroxybenzene-2-carboxylic acid and thenin acetic acid solution with 13.7 parts of2-aminol-methyl-l-methoxybenzene. The resultant intermediate isdiazotized and then coupled in approximately aqueous pyridine solutionwith 45.4 parts of the monoazo dyestuff employed in Example 1.

The thus prepared dyestuif is, after isolation and purification (byrecrystallization) followed by drying and grinding, a dark powder whichdissolves in water with an olive coloration and in concentrated sulfuricacid with a violet coloration. It dyes cotton and regenerated cellulosein olive shades which. upon aftertreatment with a salt of bivalentcopperfor example cop per sulfate in ammoniacal solution-turn towardkhaki and are improved in their fastness properties. If, as couplingcomponent, use is made of the copper complex of the aforesaid monoazodyestuff of Example 1, and the procedure set forth in the precedingparagraphs of the present example otherwise followed, the product is adyestuff which dissolves in water with a brown coloration and inconcentrated sulfuric acid with a red-brown coloration, and yieldsbrownish khaki dyeings on cotton and regenerated cellulose, the wetfastness properties of which can be improved by aftertreatment accordingto the data of Example 5.

By introducing a second atom of copper into the dyestuff by splittingoff the methoxy group, there is obtained a copper complex which yieldsolive brown dyeings of good light fastness on cotton and regeneratedcellulose. The said complex dissolves in water with an olive browncoloration and in concentrated sulfuric acid with a reddish browncoloration.

EXAMPLE 8 By coupling the diazodisazo compound employed in Example 7with the copper complex from 46.8 parts of the monoazo dyestuff employedin Example 2 in the manner described in the latter, there is obtained adyestuif which dissolves in water with an olive coloration and inconcentrated sulfuric acid with a reddish brown coloration, and dyescotton and regenerated cellulose in yellowish khaki shades of goodappearance. By aftertreatrnent with copper sulfate or according to theprocedure described in Example 5, the fastness properties of the productare improved. The copper complex compound obtained by a treatment withcopper splitting off the methoxy group possesses also valuable fastnessproperties.

EXAMPLE 9 30.3 parts of 2-aminonaphthalene-6,.8-disulfonic acid arediazotized and coupled in acetic acid solution with 10.7 parts of3-amino-1- methylbenzene. The aminoazo dyestuff is diazotized andcoupled in acetic acid solution with 13.7 parts of2-aminol-methyl-l.-1nethoxybenzene. After further diazotization, theproduct is coupled in 50% aqueous pyridine solution with the coppercomplex from parts of the mor1oazo dyestuif employed in Example 2. Theresultant tetrakisazo dyestuff is isolated and boiled for 24 hours inammoniacal solution with 25 parts of copper sulfate under reflux. Theproduct is isolated and, after having been purified byrecrystallization, dried and ground, is a dark powder which dissolves inWater with an olive coloration and in concentrated sulfuric acid with aviolet coloration, and dyes cotton or regenerated cellulose in brownishkhaki shades. The dyeings egeve aoo mawhez'a'itertreated inaccordancewith theafter treatmentdescribed in Example 5. By replacingther'initialcomponent (2-aminonaphthalene-G,8- disulfonic acidl by theequivalent amount of 2-amino-naphthalene-4,8-disulfonic' acid, andotherwise followingthe precedingly described procedure, a. 'dye'stuffof: substantially similar properties, is' obtained.

EXAMPLE. 11

By using the diazodisazo compound of. Example 6 for coupling with thecopper complex from 46.8 parts of the. monoazo. dyestuff correspondingto the formula inrapproximately 50% aqueous pyridine solution,there-is.obtained afterl working up the product in. the general manner.described in the preceding:examp1es.-.a dark powder which dissolves inwater witholive coloration and in concentrated sulfuric acid. withviolet coloration, and dyes cotton andregenerated. cellulose in brownishkhaki shades, the fastness properties of which areenhancedby'aftertreatment as described in the preceding: examples.

EXAIWPLE 12 17.3 parts, of 4aminobenzene-l-sulfonic acid are. diazotizedand the obtaineddiazo compound coupled with 38.8 parts. of the monoazo.dyestuff corresponding to the formula COOH OH HOaS in solution in 400parts of water, 200 parts of pyridine and 25 parts of concentratedaqueous ammonia. Upon completion of the coupling which takes place, theformed dyestuff is isolated and dried, whereupon a dark powder isobtained which dissolves in dilute caustic soda solution with brown-redcoloration and in concentrated. sulfuric acid with green coloration. Thenew dyestufi yields afterchromed dyeings on wool, which are of fullbrown tone.

EXAMPLE 13 16.8 parts of' -nitro-2-methoxy-l-aminocompoundeoupledr'with:883 partsvoftthe mpndazoidyestuflcorresponding to the formula.

in solution in 400-parts ofwater, 200 parts of pyridineand 25 parts ofconcentrated aqueous ammonia. Upon completion of the coupling whichtakesplace, the formed dyestufi. is isolated anddried, whereupon afldarkpowder is obtained which dissolves in dilute caustic. soda solution withbrowncoloration and inconcentrated sulfuric acidwith green coloration.Afterchromed, the dyestuff yields. deep-brownshades onlwool.

EXAMPLE 14' 16.8 parts of 5-nitro-2-methoxy-l-aminobenzene arediazotized and the resultant diazo compound coupled with 38.8 parts ofthe monoazo dyestuff which corresponds to the formula in solutioninAOOparts'of' water, 200 parts of pyridine and 25 parts of concentratedaqueous ammonia. The produced dyestuif is'filtered off directly. Dried,it is a darkpowder which dissolves in dilute caustic soda solutionwithbrownredcoloration and in concentrated sulfuric acid with greencoloration.

The new dyestuff yields afterchromeddyeings on Wool which are of deepbrown shades.

EXAMPLE 15 The tetrazo compound from 24.4 parts of 4.4-diamino-diphenyl-3-sulfonic acid is coupled with 13.8 parts of1-hydroxybenzene-2-carboxylic acid and'with'13f1 partsof2-amino-4-methyllmethoxybenzene; The resultant intermediate isthendiazotized and coupled in an aqueous solution containing 50% ofpyridine with the coppercomplex obtained from 46.8 parts of themonoazodyestufij described in Example 2: The thus'obtaineddyestuif is,following isolation and purification, converted into the complex; com:pound containing'2'atomsof copper by-means of a splitting offthe'methoxyfgroup treatment with copper sulfate. The copper complex is adark powder which dissolves in waterfwith an olive coloration and. inconcentrated sulfuric acid with a violet coloration. It; dyes cotton andregenerated cellulose in fastkhaki shades; thefastness properties ofwhichareimproved by an after-treatment as described in Example-5;

If, as second coupling component, use ismade of 18' parts of2-amino-4-acetylamino-1-meth= oxybenzene instead of2-amino-4-methyl-lmethoxybenzene, there is obtained a similar dyestufipossessing. a somewhat more brownish shade. l

The following table'sets forth additional examples of dyestuffsaccording to the invention, the procedurebeingjas described in Examples'1 benzene are diazotizcd and the obtaineddiazo to 11" and 15.

The following are formulae of representative products of the foregoingexamples.

Monoazo dyestufis corresponding to Formula B, supra, can be prepared bysubstituting an OH group for the amino group in the corre-:

spending metallized or unmetallized dyestufl of the formula V y ,IEIHzwherein one :1: stands for SOsH and the other a: for hydrogen, and :1;stands for a metallizable group, and wherein nucleus I may containadditional substituents, as previously enumerated. The replacement ofthe-amino group by the hydroxyl group can, in neutral to causticalkaline medium, be carried out in a wide variety of ways. In somecases, simple heating of the aqueous solution-of the dyestufi underreflux suffices to eifect the desired replacement; in other cases,heating for several'hours to temperatures of, for instance, 140-150 inan autoclave may be necessary. In acid medium, the aforesaid replacementcan be realized by heating for a brief period of time with dilutemineral acid.

The following example illustrates the preparation of the monoazodyestuff employed in Example 2, supra.

' EXAMPLE 25 46.7 parts of the dyestufi obtained from 1-carboxy-2-diazobenzene-4-sulfonic acid and 1-amino-7-hydroxynaphthalene-3-sulfonic acid in acetic acid solution areheated for 2 hours to 140-150" in 500 parts of 2% aqueous caustic sodasolution; The dyestuff separated by salting out and filtration, is a redpowder which dissolves in water with reddish coloration and inconcentrated sulfuric acid with brown-red coloration. It corresponds tothe formula set forth for the monoazo dyestufi in Example 2.

' EXAMPLE 26 Dyeing with a representative dyestuif according to thepresent invention may be carried out, for example as follows.

a. Dyestuffs of Examples .1 to 11 and 15 to 24:

100 parts of cotton or regenerated cellulose fiber cloth are introducedinto a dyebath containing a solution of 1 part of the dyestuif and partsof sodium sulfate in 3000 parts of Water of C. The dyebath is heatedwithin half an hour to the boil, boiled for 15 minutes and then cooledin 15 minutes to 50 C. After being rinsed, the cloth is added to a freshbath containing 3000 parts of water of 70 and 0.5 part of the coppercomplex compound of the condensation product of triethylene tetramineand dicyan diamide obtainable according to the process of the SwissPatent No. 253,709. The bath is held for half an hour at 70, then thecloth is rinsed and dried.

added in small portions.

bJDyestufis of Examples I2to'114:

100 parts of wool-rare-entered into a bath-containing a solution of 1part of the dyestufi and 10 parts of sodium sulfate in 4000 parts ofwater of 30 C. The bath is heated within an hour to the boil, whilst 2parts of acetic acid are The bath is held for an hour at the boil, then2 parts of formic acid are added. After cooling to 70 C., 1 part ofsodium bichromate is added, and the bath is held anew for half an hourat 100 C. Then the wool is rinsed and dried.

Having thus disclosed the invention, what is 1. An azo dyestuif whichcorresponds to the formula 0 wherein R stands for a radical of thebenzene series, R, R" and R stand for members selected, from the groupconsisting of monoand binuclear radicals, one :1: stands for thesulfonic acid group and the other a: for hydrogen, 7y stands for ametallizable group in ortho-position to -azo-, Me is a metal selectedfrom the group consisting of copper and chromium, n is one of theintegers 1, 2, 3 and 4, a is one of the integers 1 and 2, and b is oneof the integers 1 and 2, when a is 2, and is 1, when a is 1.

2. A process for the manufacture of an azo dyestuif comprising the stepsof coupling a diazotized amine which. corresponds to the formula and is1, when a is 1, with a monoazo dyestufl which corresponds to the formulaMen-1 wherein R stands for a radical of the benzene ,series, one :1:stands for the sulfonic acid group and the other a: for hydrogen, ystands for a metallizable group in ortho-position to -azo-, Me is ametal selected'from the group consisting of copper and chromium, and'misone of the integers l and 2, and, where m is l, treating thethus-obtained azo dyestuff with a metal-yielding agent selected from thegroup consisting of copper-yielding and chromium-yielding agents.

3. A copper complex compound of a tetrakisazo dyestuff which correspondsto the for- I mula CH4 2: I OH 1 =N-QN=N-R-N'=NQ0H 011 com coon whereinR. stands for a radical selected from the class consisting of lONHeOC Q:

a: stands for a member selected from the class consisting of hydrogenand the sulfonic acid and group, one y stands for the sulfonic acidgroup, 15

the other y being hydrogen, a stands for a member selected from theclass consisting of hydroxy and carboxy, and wherein the salicylicgrouping is free from copper.

4. The tetrakisazo dyestufi which corresponds to the formula 5. Thetetrakisazo dyestuff which corresponds to the formula 6. The tetrakisazodyestuff which corresponds to the formula 7. The tetrakisazo dyestuffwhich corresponds to the formula 8. The tetrakisazo dyestuff whichcorresponds to the formula 18 i 9. A process for the manufacture of atetrakisazo dyestufi comprising the steps of coupling a diazotizedamino-disazo compound which corresponds to the formula 00133 COOHwherein R stands for a radical selected from the class consisting of andCOOH

COOH

(I) Ha COOH COOH

amazed l9 and x stands for a member selected from the class consistingof hydrogen and the sulfonic acidgroup, with a monoazo dyestuff whichcorresponds to the formula wherein one y stands for the sulfonic acidgroup,

OCHa

20 c with the coppered monoazo dyestuff which corresponds to the formulaooo-ou o I -1 I=N OH HOaS HOaS 12. A process for the manufacture of atetrakisazo dyestuff comprising the steps of coupling the diazotizedamino-disazo' compound which corresponds to the formula with the monoazodyestuff which corresponds to the formula C O OH (RE H03 SIOKH andheating the thus-obtained a-zo dyestufi in OCHa with the copperedmonoazo dyestuff which corresponds to the formula 0 o o-ou HOaS- OsH 11.A process for the manufacture of a tetra- COOH ammoniacal aqueoussolution with a salt of bivalent copper.

13. A process for the manufacture of a tetrakisazo dyestuff comprisingthe steps of coupling the diazotized amino olisazo compound whichcorresponds to the formula OCH:

kisazo dyestuif comprising the step of coupling the diazotizedamino-disazo compound which corresponds to the formula C Ha COOH

COOH

21 22 with the monoazo dyestuff which corresponds to with the monoazodyestuff which corresponds to the formula the formula COOH on OH N=N 0H5 I N==N-- OH nms- HOaS- and heating the thus-obtained azo dyestufi inH038 ammoniacal aqueous solution with a salt of bi- 10 valent copper.

14. A process for the manufacture of a tetrakisazo dyestuff comprisingthe steps of coupling and heating the thus-obtained azo dyestuff in thediazotized amino-disazo compound which ammoniacal aqueous solution witha. salt 01' bi- OaH corresponds to the formula 15 valent copper.

on, HzNQ N=NONH. c OON=NQO H OCH: cooH HANS RUCKSTUHL. OTTO SENN. WALTERWEHRLI.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 1,901,387 Wiedemann et a1. Mar. 14, 1933 2,417,306 Krebser eta1. Mar. 11, 1947

4. THE TETRAKISAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA